Domain‐Defined Coordination Modulation of Vanadium Oxide Cathodes for Wide‐Temperature‐Tolerant Aqueous Zinc‐Ion Batteries

Layered hydrated vanadium oxides are promising cathode materials for aqueous zinc‐ion batteries but suffer from sluggish kinetics and severe V dissolution. To address this challenge, we propose a “spatial coordination domain differentiation” concept, dividing the local V coordination into two spatially functional regions. In this framework, the inner‐coordination domain (ICD) is defined as first‐shell [VO 6 ] octahedra governing orbital hybridization and structural integrity, whereas the outer‐coordination domain (OCD) comprises the interlayer gallery that accommodates guest ions and mediates long‐range electrostatic interactions. By combining x‐ray absorption, photoelectron spectroscopies, and theoretical calculations, we demonstrate that the precise pre‐intercalation of In 3+ into OCD enables targeted perturbation of ICD. Such dual‐domain regulation homogenizes [VO 6 ] octahedral distortion and promotes electron redistribution around V centers, leading to enhanced V 3d–O 2p orbital hybridization. As a result, V dissolution is effectively suppressed, while Zn 2+ /H + cointercalation kinetics are markedly accelerated. Consequently, the optimized In 0.55 V 10 O 24 ·4.35H 2 O cathode delivers specific capacities as high as 500 mAh g −1 at 60°C and 300 mAh g −1 at −60°C (0.1 A g −1 ), while maintaining capacity of 91.9% and 97.2% after 10,000 cycles at 25°C and −60°C, respectively. This work offers an orbital‐level design principle for developing high‐stability energy storage materials.